US4575544A - Ferricenium salt catalysts for vinyl ethers - Google Patents
Ferricenium salt catalysts for vinyl ethers Download PDFInfo
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- US4575544A US4575544A US06/600,627 US60062784A US4575544A US 4575544 A US4575544 A US 4575544A US 60062784 A US60062784 A US 60062784A US 4575544 A US4575544 A US 4575544A
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- composition
- ferrocene
- ferricenium
- vinyl ether
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- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 150000003839 salts Chemical class 0.000 title claims abstract description 17
- 239000003054 catalyst Substances 0.000 title 1
- 239000000203 mixture Substances 0.000 claims abstract description 39
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 9
- 229910052751 metal Inorganic materials 0.000 claims abstract description 5
- 239000002184 metal Substances 0.000 claims abstract description 5
- 229910052752 metalloid Inorganic materials 0.000 claims abstract description 5
- 150000002738 metalloids Chemical class 0.000 claims abstract description 5
- 229920000642 polymer Polymers 0.000 claims abstract description 4
- 125000005843 halogen group Chemical group 0.000 claims abstract 3
- -1 n-butyl ferrocene Chemical compound 0.000 claims description 17
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 125000002091 cationic group Chemical group 0.000 claims description 4
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 4
- 125000003107 substituted aryl group Chemical group 0.000 claims description 4
- 238000010538 cationic polymerization reaction Methods 0.000 claims description 3
- 125000002221 trityl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C([*])(C1=C(C(=C(C(=C1[H])[H])[H])[H])[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 3
- 229910017048 AsF6 Inorganic materials 0.000 claims description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical group [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical group [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052785 arsenic Inorganic materials 0.000 claims description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical group [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052797 bismuth Chemical group 0.000 claims description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical group [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 239000000460 chlorine Chemical group 0.000 claims description 2
- 229910052801 chlorine Chemical group 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 150000002560 ketene acetals Chemical class 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Chemical group 0.000 claims description 2
- 238000010526 radical polymerization reaction Methods 0.000 claims description 2
- 150000003254 radicals Chemical class 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- 101150108015 STR6 gene Proteins 0.000 claims 1
- 125000001153 fluoro group Chemical group F* 0.000 claims 1
- 229920005989 resin Polymers 0.000 abstract description 7
- 239000011347 resin Substances 0.000 abstract description 7
- 101100386054 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) CYS3 gene Proteins 0.000 abstract 1
- 101150035983 str1 gene Proteins 0.000 abstract 1
- 230000006698 induction Effects 0.000 description 12
- 229960000834 vinyl ether Drugs 0.000 description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 11
- 239000003999 initiator Substances 0.000 description 11
- 229910052760 oxygen Inorganic materials 0.000 description 11
- 239000001301 oxygen Substances 0.000 description 11
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 239000005297 pyrex Substances 0.000 description 6
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- NJXYTXADXSRFTJ-UHFFFAOYSA-N 1,2-Dimethoxy-4-vinylbenzene Chemical compound COC1=CC=C(C=C)C=C1OC NJXYTXADXSRFTJ-UHFFFAOYSA-N 0.000 description 2
- BOXSCYUXSBYGRD-UHFFFAOYSA-N cyclopenta-1,3-diene;iron(3+) Chemical class [Fe+3].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 BOXSCYUXSBYGRD-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 150000004820 halides Chemical group 0.000 description 2
- 239000002198 insoluble material Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- MWZJGRDWJVHRDV-UHFFFAOYSA-N 1,4-bis(ethenoxy)butane Chemical compound C=COCCCCOC=C MWZJGRDWJVHRDV-UHFFFAOYSA-N 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- FJUFINOZWSTZEZ-UHFFFAOYSA-N 5-butylcyclopenta-1,3-diene;iron(2+) Chemical compound [Fe+2].CCCCC1=CC=C[CH-]1.CCCCC1=CC=C[CH-]1 FJUFINOZWSTZEZ-UHFFFAOYSA-N 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 229920002681 hypalon Polymers 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- KKFHAJHLJHVUDM-UHFFFAOYSA-N n-vinylcarbazole Chemical compound C1=CC=C2N(C=C)C3=CC=CC=C3C2=C1 KKFHAJHLJHVUDM-UHFFFAOYSA-N 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F16/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F16/12—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
Definitions
- the invention is a composition of a vinyl ether resin and at least one ferricenium salt of the formula: ##STR2## where R 1 , R 2 , R 3 and R 4 are the same or different H or alkyl groups or a linkage to a polymer backbone; M is a metal or metalloid; X is a halide; and n is an integer equal to 1 plus the valency of M.
- a further aspect of the invention is a method of making the inventive compositions by generating the ferricenium salt in situ by addition of a trityl salt to a composition of vinyl ether monomer and a ferrocene compound.
- a still further aspect of the invention is a method of curing vinyl ether resins by adding a ferricenium salt, as defined above, to a vinyl ether composition.
- a particularly surprising feature of this aspect of the invention is the fact that while vinyl ethers are known to polymerize only by a cationic method and cationic polymerizations are not known to be sensitive to atmospheric oxygen, the presence or absence of oxygen plays a key role in the polymerization of the inventive compounds. When exposed to atmospheric oxygen the inventive compositions polymerize much more rapidly than they do when steps are taken to minimize or exclude exposure to atmospheric oxygen.
- the vinyl ether resins useful in the inventive compositions may be represented by the formulas:
- G is a mono or multivalent radical free of groups, such as amino, substituted amino or phenol, which interfere with cationic or free radical polymerization;
- n is an integer greater than or equal to 1;
- R 1 and R 2 are selected from H, alkyl, substituted alkyl, aryl, and substituted aryl;
- R 3 is selected from alkyl, substituted alkyl, aryl, and substituted aryl;
- X is a hydrocarbonyl group of 1-5 carbon atoms.
- the inventive compositions will contain a substantial proportion of polyfunctional vinyl ether resins in order to produce solid cured products.
- Ferricenium salts may be derived from the ferrocene or alkyl substituted ferrocenes such as n-butyl ferrocene, t-octyl ferrocene 1,1'-dibutyl ferrocene, and poly(vinyl ferrocene).
- alkyl substituted ferrocenes such as n-butyl ferrocene, t-octyl ferrocene 1,1'-dibutyl ferrocene, and poly(vinyl ferrocene).
- a variety of methods for generating ferricenium salts from ferrocenes are known in the art.
- One useful method of generation is to add a trityl salt, such as triphenyl hexachloroantimonate, to ferrocene dissolved in a suitable solvent.
- the trityl salt/ferrocene product may be prepared separately and added subsequently to a vinyl ether monomer composition.
- a dark blue precipitate forms immediately. This precipitate is air stable. Analysis shows the blue precipitate to be an equimolar mixture of ferricenium tetrachloroantimonite and ferricenium hexachloroantimonate.
- M denotes an atom of a metal or metalloid selected from antimony, phosphorus, boron, arsenic, tin, or bismuth;
- X is a halide, preferably fluorine or chlorine; and
- n is an integer equal to 1 plus the valency of M.
- complex anions include BF 4 --, PF 6 --, AsF 6 --, SbF 6 --, SnCl 5 --, SbCl 4 --, SbCl 6 --, etc.
- ferricenium salts do not initiate cure of other types of cationically curable monomers and resins, with the single apparent exception of N-vinyl carbazole and its analogs. Epoxy resins and 3,4-dimethoxystyrene are not cured by ferricenium salts.
- the concentration of ferricenium salt in the inventive compositions is usefully in the range of 0.01%-5% by weight of the composition.
- BDVE 1,4-butanediol divinyl ether
- BDVE n-butyl ferricenium tetrachloroantimonite and n-butyl ferricenium hexachloroantimonate
- BDVE t-octyl ferricenium tetrachloroantimonite and t-octyl ferricenium hexachloroantimonate
- BDVE 1.0 gram of BDVE was poured into a 12 mm ⁇ 75 mm Pyrex test tube and 0.1 grams of a 1 percent solution of ferricenium hexafluorophosphate in acetonitrile was added. No special precautions were taken to exclude atmospheric oxygen. The induction time was 2260 seconds.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
A curable composition of a vinyl ether resin and at least one ferricenium salt of the formula: ##STR1## where R1, R2, R3 and R4 are the same or different H or alkyl groups or a linkage to a polymer backbone; M is a metal or metalloid; X is a halide; and n is an integer equal to 1 plus the valency of M.
Description
Numerous methods of polymerizing vinyl ethers are known, including protonic acids, metal halides and stable carbocation salts. References describing cationic cure systems for vinyl ether resins include: U.S. Pat. Nos. 3,196,098; 4,069,056; 4,192,924; and 4,416,752.
In a copending application of the same inventors herein, filed Feb. 21, 1984, Ser. No. 581,857, there are described novel acrylic monomer/peroxy initiator compositions which utilize certain ferrocenium salts as novel polymerization activators. These same ferricenium salts are useful as initiators in the vinyl ether compositions of the present invention.
The invention is a composition of a vinyl ether resin and at least one ferricenium salt of the formula: ##STR2## where R1, R2, R3 and R4 are the same or different H or alkyl groups or a linkage to a polymer backbone; M is a metal or metalloid; X is a halide; and n is an integer equal to 1 plus the valency of M.
A further aspect of the invention is a method of making the inventive compositions by generating the ferricenium salt in situ by addition of a trityl salt to a composition of vinyl ether monomer and a ferrocene compound.
A still further aspect of the invention is a method of curing vinyl ether resins by adding a ferricenium salt, as defined above, to a vinyl ether composition. A particularly surprising feature of this aspect of the invention is the fact that while vinyl ethers are known to polymerize only by a cationic method and cationic polymerizations are not known to be sensitive to atmospheric oxygen, the presence or absence of oxygen plays a key role in the polymerization of the inventive compounds. When exposed to atmospheric oxygen the inventive compositions polymerize much more rapidly than they do when steps are taken to minimize or exclude exposure to atmospheric oxygen.
The vinyl ether resins useful in the inventive compositions may be represented by the formulas:
(CH.sub.2 ═CH--O--CH.sub.2).sub.n --G
(CH.sub.2 ═CH--O--C.sub.6 H.sub.4).sub.n --G
(CH.sub.2 ═CH--O--CR.sup.1 ═CR.sup.2).sub.n --G
CH.sub.2 ═CH--O--C.tbd.C).sub.n --G
or ketene acetals such as those of the formulas: ##STR3## where G is a mono or multivalent radical free of groups, such as amino, substituted amino or phenol, which interfere with cationic or free radical polymerization; n is an integer greater than or equal to 1; R1 and R2 are selected from H, alkyl, substituted alkyl, aryl, and substituted aryl; R3 is selected from alkyl, substituted alkyl, aryl, and substituted aryl; and X is a hydrocarbonyl group of 1-5 carbon atoms. In general, the inventive compositions will contain a substantial proportion of polyfunctional vinyl ether resins in order to produce solid cured products.
Ferricenium salts may be derived from the ferrocene or alkyl substituted ferrocenes such as n-butyl ferrocene, t-octyl ferrocene 1,1'-dibutyl ferrocene, and poly(vinyl ferrocene). A variety of methods for generating ferricenium salts from ferrocenes are known in the art. One useful method of generation is to add a trityl salt, such as triphenyl hexachloroantimonate, to ferrocene dissolved in a suitable solvent.
The trityl salt/ferrocene product may be prepared separately and added subsequently to a vinyl ether monomer composition. Thus, when ferrocene and triphenylmethylhexachloroantimonate are mixed under nitrogen in dry CH2 Cl2 a dark blue precipitate forms immediately. This precipitate is air stable. Analysis shows the blue precipitate to be an equimolar mixture of ferricenium tetrachloroantimonite and ferricenium hexachloroantimonate.
The counter ions of ferricenium salts have the formula
MX.sub.n --
where M denotes an atom of a metal or metalloid selected from antimony, phosphorus, boron, arsenic, tin, or bismuth; X is a halide, preferably fluorine or chlorine; and n is an integer equal to 1 plus the valency of M. Examples of such complex anions include BF4 --, PF6 --, AsF6 --, SbF6 --, SnCl5 --, SbCl4 --, SbCl6 --, etc.
An unusual aspect of the present invention is that the ferricenium salts do not initiate cure of other types of cationically curable monomers and resins, with the single apparent exception of N-vinyl carbazole and its analogs. Epoxy resins and 3,4-dimethoxystyrene are not cured by ferricenium salts.
The concentration of ferricenium salt in the inventive compositions is usefully in the range of 0.01%-5% by weight of the composition.
The invention may be illustrated by the following nonlimiting examples:
2.0 grams of 1,4-butanediol divinyl ether (BDVE) was poured into a 12 mm×75 mm Pyrex test tube. A weighed amount of an equimolar mixture of ferricenium tetrachloroantimonite and ferricenium hexachloroantimonate (designated Initiator A) was added to the BDVE, a stopwatch was started and the mixture stirred vigorously for a few seconds. The tube was then placed in a rack and observed. No precautions to exclude atmospheric oxygen were taken. A period of inactivity during which the viscosity of the mixture remained unchanged was followed by a rapid and violent reaction which yielded a hard insoluble material after a few seconds. The length of the induction time for a variety of reaction conditions is listed in Table 1.
TABLE 1
______________________________________
Induction
BDVE, g Initiator A, g
time, sec.
______________________________________
2.0 0.020 198
2.0 0.010 235
2.0 0.005 572
2.0 0.003 1860
______________________________________
3.0 grams of a commercially available chlorosulfonated rubber (DuPont Hypalon 20) was dissolved in 10.0 grams of BDVE. 2.0 grams of this mixture was poured into a 12 mm×75 mm Pyrex test tube, and 0.010 grams of Initiator A was added to the mixture. A stopwatch was started and the mixture was stirred for a few seconds. No precautions to exclude atmospheric oxygen were taken. After an induction time of 250 seconds during which there was no observable change in the viscosity of the mixture, a rapid and violent reaction occurred yielding a hard insoluble material.
1.0 gram of acetonitrile was poured into a 12 mm×75 mm Pyrex test tube, and 1.0 gram of a vinyl ether as specified in Table 2 was added. After this mixture was stirred for a few seconds, 0.010 grams of Initiator A was added and a stop watch was started. The mixture was again stirred for a few seconds. No precautions were taken to exclude atmospheric oxygen. After an induction period during which no observable change in the viscosity of the solution occurred, a rapid and violent reaction ensued followed by the formation of an oily precipitate. The precipitate was characterized as a quantitative yield of low molecular weight vinyl ether polymer.
TABLE 2
______________________________________
Vinyl Ether (g)
Induction Time, Sec
______________________________________
Ethyl (1.0) 354
n-butyl (1.0) 567
BDVE (1.0) 698
______________________________________
Equal amounts of acetonitrile (2.0 grams) and n-butyl vinyl ether (1.5 grams) were added to two 12 mm×75 mm Pyrex test tubes. Into both mixtures 0.010 grams of Initiator A were added with stirring for a few seconds. The first test tube was then flushed with nitrogen and sealed, while no precautions to exclude atmospheric oxygen were taken with the second test tube. The contents of the second tube underwent a violent and rapid reaction after an induction time of 10-15 minutes, while the contents of the tube sealed under nitrogen underwent a similar reaction after an induction time of 75 minutes. In both cases an oily precipitate formed.
1.0 gram of BDVE was poured into a 12 mm×75 m test tube, and 0.005 grams of an equimolar mixture of n-butyl ferricenium tetrachloroantimonite and n-butyl ferricenium hexachloroantimonate (Initiator B) was added and stirred for a few seconds. No special precautions were taken to exclude atmospheric oxygen. The induction time was 219 seconds. The experiment was repeated with 2.0 grams of BDVE and 0.005 grams of Initiator B. The induction time was 269 seconds.
2.0 grams of BDVE was poured into a 12 mm×75 mm Pyrex test tube, and 0.010 grams of an equimolar mixture of t-octyl ferricenium tetrachloroantimonite and t-octyl ferricenium hexachloroantimonate (Initiator C) was added and stirred for a few seconds. No special precautions were taken to exclude atmospheric oxygen. The induction time was 762 seconds. The experiment was repeated with 2.0 grams of BDVE and 0.005 grams of Initiator C. The induction time was 1845 seconds.
1.0 gram of BDVE was poured into a 12 mm×75 mm Pyrex test tube and 0.1 grams of a 1 percent solution of ferricenium hexafluorophosphate in acetonitrile was added. No special precautions were taken to exclude atmospheric oxygen. The induction time was 2260 seconds.
Claims (9)
1. A curable composition consisting essentially of a mixture of at least one vinyl ether monomer and a ferricenium salt represented by the formula: ##STR4## where R1, R2, R3, and R4 are the same or different H or alkyl groups or a linkage to a polymer backbone, M is a metal or metalloid; X is a halide and n is an integer equal to 1 plus the valency of M.
2. A composition in claim 1 formed by addition of a trityl salt to a composition comprising a vinyl ether monomer and a ferrocene.
3. A composition as in claim 1 wherein M is selected from arsenic, antimony, phosphorus, boron, tin or bismuth.
4. A composition as in claim 1 where X is fluorine or chlorine.
5. A composition as in claim 3 wherein MX-- is selected from BF4 --, PF6 --, AsF6 --, SbF6 --, SnCl5 --, SbCl4 --, SbCl6 --.
6. A composition as in claim 5 wherein MXn -- is SbCl6 --, SbCl4 --, PF6 --, or mixtures thereof.
7. A composition as in claim 1 wherein the ferricenium salt is a salt of ferrocene, n-butyl ferrocene, t-octyl ferrocene, 1,1-dibutyl ferrocene or poly(vinyl ferrocene).
8. A composition as in claim 1 wherein the vinyl ether is represented by one of the formulas:
(CH.sub.2 ═CH--O--CH.sub.2).sub.n --G
(CH.sub.2 ═CH--O--C.sub.6 H.sub.4).sub.n --G
(CH.sub.2 ═CH--O--CR.sup.1 ═CR.sup.2).sub.n --G
CH.sub.2 ═CH--O--C.tbd.C).sub.n --G
or ketene acetals such as those of the formulas: ##STR5## where G is a mono or multivalent radical free of groups, such as amino, substituted amino or phenol, which interfere with cationic or free radical polymerization; n is an integer greater than or equal to 1; R1 and R2 are selected from H, alkyl, substituted alkyl, aryl, and substituted aryl; R3 is selected from alkyl, substituted alkyl, aryl, and substituted aryl; and X is a hydrocarbonyl group of 1-5 carbon atoms.
9. A method of curing a composition containing essentially of vinyl ether comprising adding alone or in a solvent a ferricenium salt of the formula: ##STR6## where R1, R2, R3 and R4 are the same or different H or alkyl groups or a linkage to a polymeric backbone, M is a metal or metalloid; X is a halide and n is an integer equal to 1 plus the valency of M, to said composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/600,627 US4575544A (en) | 1984-04-16 | 1984-04-16 | Ferricenium salt catalysts for vinyl ethers |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/600,627 US4575544A (en) | 1984-04-16 | 1984-04-16 | Ferricenium salt catalysts for vinyl ethers |
| EP85309412A EP0226675B1 (en) | 1985-12-23 | 1985-12-23 | Ferricenium salt catalysts for vinyl ethers |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US4575544A true US4575544A (en) | 1986-03-11 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US06/600,627 Expired - Lifetime US4575544A (en) | 1984-04-16 | 1984-04-16 | Ferricenium salt catalysts for vinyl ethers |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US4575544A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4808638A (en) * | 1986-10-14 | 1989-02-28 | Loctite Corporation | Thiolene compositions on based bicyclic 'ene compounds |
| US5047445A (en) * | 1988-06-20 | 1991-09-10 | Victor Company Of Japan, Ltd. | Electroconductive polymeric material |
| WO2006052427A1 (en) * | 2004-11-05 | 2006-05-18 | Dow Global Technologies Inc. | Highly soluble ferrocenyl compounds |
| JP2019094367A (en) * | 2017-11-17 | 2019-06-20 | 丸善石油化学株式会社 | Production method of vinyl ether polymer using onium salt |
| WO2020170295A1 (en) * | 2019-02-18 | 2020-08-27 | 丸善石油化学株式会社 | Method for producing vinyl ether polymer using onium salt |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3855040A (en) * | 1972-07-03 | 1974-12-17 | Loctite Corp | Anaerobic compositions |
| US4525232A (en) * | 1984-04-16 | 1985-06-25 | Loctite (Ireland) Ltd. | Polymerizable acrylic compositions having vinyl ether additive |
| US4525553A (en) * | 1984-02-21 | 1985-06-25 | Loctite (Ireland) Limited | Acrylic polymerization catalysts containing ferricenium salts |
-
1984
- 1984-04-16 US US06/600,627 patent/US4575544A/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3855040A (en) * | 1972-07-03 | 1974-12-17 | Loctite Corp | Anaerobic compositions |
| US4525553A (en) * | 1984-02-21 | 1985-06-25 | Loctite (Ireland) Limited | Acrylic polymerization catalysts containing ferricenium salts |
| US4525232A (en) * | 1984-04-16 | 1985-06-25 | Loctite (Ireland) Ltd. | Polymerizable acrylic compositions having vinyl ether additive |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4808638A (en) * | 1986-10-14 | 1989-02-28 | Loctite Corporation | Thiolene compositions on based bicyclic 'ene compounds |
| US5047445A (en) * | 1988-06-20 | 1991-09-10 | Victor Company Of Japan, Ltd. | Electroconductive polymeric material |
| WO2006052427A1 (en) * | 2004-11-05 | 2006-05-18 | Dow Global Technologies Inc. | Highly soluble ferrocenyl compounds |
| US20080097056A1 (en) * | 2004-11-05 | 2008-04-24 | Rosen Robert K | Highly Soluble Ferrocenyl Compounds |
| US7645893B2 (en) | 2004-11-05 | 2010-01-12 | Dow Global Technologies, Inc. | Highly soluble ferrocenyl compounds |
| JP2019094367A (en) * | 2017-11-17 | 2019-06-20 | 丸善石油化学株式会社 | Production method of vinyl ether polymer using onium salt |
| WO2020170295A1 (en) * | 2019-02-18 | 2020-08-27 | 丸善石油化学株式会社 | Method for producing vinyl ether polymer using onium salt |
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